Process for the separation of an unsaturated hydrocarbon from a hydrocarbon mixture



PatcntedDec. 25,1945

PROCESS FOR THE SEPARATION or AN UN- SATURATED HYDROCARBON FROM A BY- DROGARBON MIXTURE Bernard S. Friedman and Russell F. Stedman,

Chicago, Ill., assignors to Universal Oil Products Company, Chicago, Ill., a corporation of Delaware No Drawing.

Application September 28, 1942, Serial No. 459,941

13 Claims. (Cl. 260-677) This invention relates to an improvement in processes for the separation of mixtures containing two or more different components.

It is particularly-applicable to the treatment of hydrocarbon mixtures for the separation oi unsaturated from less unsaturated hydrocarbons. In another modification, the invention may be utilized for the separation of branched chain unsaturated compounds and particularly hydrocarbons from mixtures containing the same and less unsaturated compounds and particularly hydrocarbons, as well as for the separation of lower boiling olefins from higher boiling olefins.

The invention may be utilized in connection with the extraction of a great many types of compounds and the following include only afew examples. The mixtures which may be treated in the present invention may be normally gaseous, normally liquid or mixtures of both normally gaseous and normally liquid compounds. In one embodiment, the invention may be utilized for the separation of, for example, butylenes from butane or for the separation of any olefinic hydrocarbon from its corresponding paratfinic hydrocarbon. Similarly, the invention may be utilized for the separation of butadiene from butylenes and/or butanes or for the separation of any diolefinic hydrocarbon from its corresponding ,mono-olefinic and/or paraffinio hydrocarbon, as well as-for the separation of poly-'- olefinic hydrocarbons. Also, the invention may be utilized for the separation of styrene from ethylbenzene or for the separation of any aromatic hydrocarbon containing an unsaturated side chain from itscorresponding aromatic hydrocarbon containing a saturated side chain.

In still another modification, the invention may be utilized for the separation of mixtures of olefinic hydrocarbons from mixturesofparafline hydrocarbons, such as, for example, the removal of olefinic hydrocarbons from a gasoline or other distillate containing the same, in order to leave a paraflinic product which, in the case of gasoline, will comprise a distillate which is particularly suitable for use in aviation fuel. Another application of the present process is in the purification of various hydrocarbon fractions. example, in the isomerization of paraffinic hydrocarbons, it has been found that the presence of substantial amounts of olefins is undesirable when employing metal halide catalysts, and the In still another modification, the invention may be utilized for the separation of isobutylene by virtue of preferential solubility from mixtures containing the same and normal butylene, or for the separation of any branched chain olefin from its corresponding straight chain olefin. Further, the invention may be utilized for the separation of lower boiling olefinic hydrocarbons by preferential solubility from higher boiling oleflnic 1137-,- drocarbons. For example, mixtures containing butylene, butane, amylene and pentane cannot separating agent of the present invention'may be For process of the present invention may. be utilized be readily separated by purely fractionationmeans in order to recover the butylenes. The

It is understood that the results obtained by the treatment of these various mixtures win not necessarily be equivalent.

The charging stock is preferably given a preliminary treatment to remove any sulfur compounds which may be contained therein, in order to avoid any deleterious effect which the sulfur may exert on the separating agent of the present invention. This preliminary treatment may comprise, for example, a caustic wash to remove hydrogen sulphide and/or a more severe treatment-to remove other sulfur compounds.

The present invention is characterized by a novelseparating agent which broadly comprises a water or organic soluble salt of silver dissolved in an aqueous or anhydrous solution of a non-basic and preferably. neutral water-soluble organic compound. The use of aqueous solutionsof'silver salts and particularly silver nitrate has heretofore been proposed for the separation of hydrocarbons. However, these aqueous solutions in some cases have a low. solvent powerfor hydrocarbons. By solvent power, it is meant the amount of hydrocarbons dissolved in the separating agent. For example, our experiments have indicated that a 40 weight per cent silver nitrate solution in water will dissolve only '7' cc. of styrene in cc. of the solution. This, it is noted, is a very low solubility, and the present invention discloses an improved method of increasing the solubility of the hydrocarbons in silver salt solutions.

We have found that by dissolving a silver salt in an aqueous or anhydrous solution ofa nonbasic and preferably neutral water-soluble organic compound, the solvent power ofthe separating agent is greatly enhanced. For example,

silicate. fluoride, etc.

2 a 40 weight per cent silver nitrate solution in ethylene glycol will dissolve 36 cc. of styrene in 100 cc. of the solvent. This. may be compared to the 7 cc. of hydrocarbons dissolved in the 40 per cent silver: nitrate-water solution.

Water or organic soluble silver salts which may be utilized in accordance with the present invention include' the nitrate. perchlorate, fluo- Care must be utilized in connection with the perchlorate in order to avoid the presence of perchloric acid, which might cause explosions. It is understood, of course, that the results obtained by the use of the different salts of silver will not necessarily be equivalent. The water soluble organic compounds which may be used in accordance with the present invention should have a neutral reaction and should not be basic. The basic compounds form undesired reaction products with the silver ion and therefor interfere with the desired separation. Of the neutral water-soluble compounds which may be utilized, the glycols, glycol 'ethers and nitriles are preferred. Included in the glycols are ethylene glycol and its water-soluble homologs. Methyl Cellosolve or 2-methoxy-ethanol is an example of a water-solubl ether of ethylene glycol.

Of the water soluble nitriles, acetonitrile and succinonitrile are typical examples. It is, of course, within the scope of the invention to utilize the homologs .as well as the hydroxy, sulfonic or carboxy derivatives of these compounds, provided that they are water soluble and nonbasic. Likewise it is within the scope of the invention to utilize mixtures of two or more of these organic compounds, when desired. It is understood that the results obtained by the use of these various alternative compounds are not necessarily equivalent.

Our experiments have indicated that, in certain cases, improved results are obtained when the separating agent contains water in addition to the silver salt and water soluble organic compound. The amount of water to be utilized in the separating agent will depend upon the particular silver salt and the particular organic compound being employed. The exact amount of water to add to any particular solution to produce optimum results can easily be determined by a few simple solubility tests in the laboratory. I

Our experiments have also indicated that best results are obtained when employing highconcentrationsof the silver salt. However, the concentration of the silver salt which may be utilized in the separating agent will be limited primarily by its solubility in the particular organic compound utilized. To itemize the specific proportions of the many possible solutions which may be prepared in accordance with the present invention would make an extremelylengthy list and would extend the present specifications beyond a reasonable length. In view of the fact that these. solubilities may be readily determined in the laboratory, it is not specified in detail herein, although the examples cited in'the latter part of this specification will give a few typical examples of the preferred separating agent.

It is recognized that the selectivity-that is,

- the absorption of one or more types of components preferentially to another or other types of components-may, in certain cases, be lessthan when employing aqueous solution of the silver salt. However, the greatly increased solvent power will, in most instances, more than compensate for the decrease in selectivity when considered from the viewpoint of economical and practical operation.

The temperatures to be employed in the extraction step of the process will depend primarily upon the particular compounds being treated, and the temperature may range from sub-atmospheric up to 150 F. or more. In general, the temperature should be below about 150 F., in order to avoid undesired reactions which may occur at the higher temperatures. Although atmospheric, sub-atmospheric or super-atmospheric pressures may be employed, it is generally preferred to employ sufiicient super-atmospheric pressure in order to maintain the hydrocarbons in substantially liquid phase. However, when operating with mixtures containing ethylene, it

may not be economical to employ sufllcient pressures to obtain liquid phase operation and, in

such cases. the process may be conducted in vapor or mixed phase, but not necessarily with equivalent results. I

Any suitable type of apparatus may be employed for effecting the desired separation, and this may take the form of a single or multiple stage operation. Batch operations may be effected by contacting the hydrocarbon mixture and separating agent in a vessel which is maintained at the proper temperature and pressure conditions and which preferably is provided with some sort of stirring mechanism. After satisfactory mixing has been accomplished, the mixture may be allowed to settle into an extract and rafflnate phase and each of these phases may be separately withdrawn.

Continuous operations are well known in the art at the present time and may take the form of one or more vessels or zones which do or do not contain packing material such as clays, gravel. synthetic materials, etc., and/or fractionating means such as baille plates, bubble trays, or the like. Either concurrent or countercurrent flow may be employed and the mixture may then be allowed to settle in either the same or different zones in order to separate an extract layer and a raffinate layer. These layers are then separately withdrawn.

After separation of these layers, the hydrocarbons may be recovered irom the separating agent by any suitable'means. One satisfactory method is by heating to a higher temperature in order to distill the hydrocarbons, However, this method of'recovery must not be used when undesired reactions will occur at the higher temperatures due to the catalytic action exerted by the separating agent. Another suitable method of recovering the hydrocarbons from the separating agent is by'reducing the pressure of the extract phase, for example, in order to liberate the hydrocarbons. This method may have particular application when the absorption step of the process is conducted under high pressures. In some cases it may be desired to employ both an increased temperature and reduced pressure in the desorption or recovery stage. Another suitable method is the use of a secondary solvent which is immiscible with the separating agent in order to dissolve the hydrocarbons in the secondary solvent, The secondary solvent is preferably of either higher or lower boiling range than the hydrocarbons so that the hydrocarbons may be subsequently readily separated therefrom by fractionation means. It is also within the scope of the invention to recover the hydrocarbons from the separating agent by multiple stage desorption conducted at increasing temperatures and/or decreasing pressures. In this manner, the first portions so desorbed or released will be richer in one type of compound than will be the subsequently desorbed portions.

the mixture with a solution of a silver salt in a water-soluble organic compound selected from the group consisting of glycols'and glycol ethers.

2. A process for separating olefins from par- We claim as our invention:

1. A process for the separation of an unsaturated hydrocarbon from' a hydrocarbon mixture containing the same which comprises contacting It is understood, however, that the heretofore 5 afflns which comprise contactlnga, pm specified methods oi recovering the hydrocarbons taining olefinic and paraifinic hydrocarbons with from the separatingagent will not necessarily be a solution of a silver salt in a water-soluble orequivalent in their effectiveness and that the game compound selected from the group consistchoice as to the particular one to be used in any ing oi glycols and glycol ethers. given instance will depe d primarily upon the 3. A process such as is defined in claim 1 where- I type of hydrocarbons undergoing treatment. in said organic compound comprises a glycol.

After separation of the hydrocarbons, the sep- 4. A process such as is defined in claim 1 arating agent may of course be recycled to the wherein said organic compound comprises ethyl-, extraction step for further use therein or, when ene glycol. desired, the separating agent may be utilized for 5. A process suchas defined in claim 1 whereextracting the unsaturated compounds from the in said organic compound comprises a-glycol rafii-nate layer or from other hydrocarbon mixether. tures in the same or'diflerent zones. 6. A process such as is defined in claim 1 The following examples are introduced for the wherein said organic compound comprises 2- purpose of further illustrating the novelty and methoxy-ethanol. utility of the presentinvention but not with the 7. A process such as is defined in claim 1- intention of unduly limi in th S'am wherein said solution contains water.

Emmple mixture mp n 40 P r nt 8. A process for separation of diolefins from styrene and 60 per cent ethylbenzene was conolefins which comprises contacting a mixture tacted with an equal volume 01 silver nitrate socontaining said diolefins and olefins with a seplution in (1) 50 percent Wat r. 2) 8 P rc nt -arating agent comprising a solution of a waterhylene gly l, and (3) 41 percent yl ne glysoluble salt of silver in a water-soluble organic col and 10 percent water. There were dissolved compound selected from the group consistingof from the blend, 4.4, 12.4 and 10.1 cc. of styrene. glycols and glycol ethers. per 100 cc. of silver nitrate solution respectively. 9. A process for separation of vinyl aromatics Example Solution of nt by weight from alkylate aromatics which comprises iconof silver nitrate in acetonitrile dissolved 127 cc. tacting a mixture containing said vinyl aromatics of styrene per 100 cc. of silver nitrate solution and alkylatedaromatics with a separating agent from a pure styrene fraction, whereas a 70 per-- comprising a solution ofa water-soluble salt of cent by weight silver nitrate solution in water silver in a water-soluble organic compound sedissolved 38 cc. lected from the group consisting of .glycols and Example 3.A mixture of 17 percent cycloglycol ethers. hexane and 83 percent hexene-l .was contacted 10. A process for removing unsaturated hydrowith a solution of (1) 70 percent by weight of carbons from ahydrocarbon distillate which comsilver nitrate in water, (2) 42 percent by weight 40 prises contacting the distillate with a solution of of silver nitrate in ethylene glycol and (3) 49 a silver salt in a water-soluble organic compound percent by weight of silver nitrate in 41 percent selected from the group consisting of glycols and ethylene glycol and 10 percent water. There glycol ethers. were dissolved from the blend, 4.9, 26.7, and 24.5 11. The process as defined in claim 10 further cc. of olefins comprising 28 percent, 24 percent 45 characterized in that said distillate comprises oleand 27 percent cyclohexene, per cc. of silver finic gasoline. nitrate solutionrespectively. 12. A process for separating olefins from par- Emample 4.A mixture comprising 22.5 perafiins whichcomprisescontacting a mixture concent butadiene, 27.7 percent n-butylene and 49.8 tainlng olefinic and paraifinic hydrocarbons with percent n-butane was extracted with the i'ollow- 50 a solution of a silver salt in a glycol. ing separating agents to give the results indi 13. A process for separating olefins from parcated below. afiins which comprises contacting a mixture con- Percmt oj'buladims Percent ofn-butulme Percent of 'n-butane Cc. oi unsaturated liquid Separating agent olefins dis- Inextract Inramnatc In extract Inraflinate In extract Inraflinate fggg";

\ solution 42.8percentailvernitrateinethyleneglycol 60.4 19.2 85.2 26.6 3.8 54.2 16.2 74.1 silver nitrate in aceto-nitrile 62. 4 16. 6 36. 6 26. 3 l. 0 67. 1 25. 6 55.3 percent silver nitrate, 36.8% ethylene glycol, 8.9%

wafer 660 '232 280 10.8 539 taining olefinic and parafiinic hydrocarbons with a solution 0! a silver alt in a glycol ether. 

